Readily removable opaque protective layers and articles containing them

ABSTRACT

READILY REMOVABLE OPAQUE COATINGS OVER ONE OR BOTH SIDES OF A PHOTOGRAPHIC OR RADIOGRAPHIC FILM, WHICH COATINGS CAN BE REMOVED IN A SINGLE PIECE, CAN BE MANUFACTURED BY APPLYING OVER THE FILM A MULTILAYER COATING COMPOSITION COMPRISING (A) A FIRST &#34;BARRIER&#34; LAYER CONTAINING ONE OR MORE WATER SOLUBLE POLYMERS THAT ARE COMPATIBLE WITH GELATIN AND THAT ADHERE TENACIOUSLY TO THE &#34;OPAQUE&#34; LAYER (B) AND (B) AN &#34;OPAQUE&#34; LAYER (OVER THE &#34;BARRIER LAYER&#34;) COMPOSED OF A BLEND OF FINELY DIVIDED CARBON AND AT LEAST ONE WATER-INSOLUBLE POLYMER.   THE &#34;OPAQUE&#34; LAYER MUST BE FAIRLY PERMEABLE TO WATER, SO THAT WHEN IT IS DESIRED TO REMOVE THE &#34;OPAQUE&#34; COATING, THE FILM CAN SIMPLY BE IMMERSED IN WATER. WITHIN A VERY SHORT TIME THE &#34;OPAQUE&#34; LAYER FALLS AWAY FROM THE FILM IN A SINGLE PIECE, RATHER THAN IN SMALL TROUBLESOME FLAKES.

July.18, 1972 J. F. BISHOP ErAL 3,677,790

READILY REMOVABLE OPAQUE PROTECTIVE LAYERS AND ARTICLES CONTAINING THEMOriginal Filed Oct. 28, 1968 Z/ Y SENS/T/ZED LA YER POLYMER/C FILM BASE//-////7( GEL PELLO/D L\ BARR/El? LAYER OPA0UE LAYER SENS/T/ZED LAYERPOL YMER/C F/LM BASE GEL PELLO/D BARR/ER LAYER OPAOUE LAYER A/VTl-FR/CT/ON LAYER JOHN F. BISHOP WALKER F. HUNTER MART/N E. ROWLEY INVENTO A TTORNEY United States Patent O 3,677,790 READILY REMOVABLE OPAQUEPROTECTIVE LAYERS AND ARTICLES CONTAINING THEM John F. Bishop, Webster,and Walker F. Hunter, Jr.,

and Martin E. Rowley, Hilton, N.Y., assignors to Eastman Kodak Company,Rochester, N.Y.

Application Oct. 28, 1968, Ser. No. 788,109, now Patent No. 3,598,591,dated Aug. 10, 1971, which is a continuation-impart of application Ser.No. 645,032, June 9, 1967. Divided and this application Aug. 12, 1970,Ser. No. 63,292

Int. Cl. G03c 1/84 US. Cl. 117-333 5 Claims ABSTRACT OF THE DISCLOSUREReadily removable opaque coatings over one or both sides of aphotographic or radiographic film, which coatings can be removed in asingle piece, can be manufactured by applying over the film a multilayercoating composition comprising (a) a first barrier layer containing oneor more water soluble polymers that are compatible with gelatin and thatadhere tenaciously to the opaque layer (b) and (b) an opaque layer (overthe barrier layer) composed of a blend of finely divided carbon and atleast one water-insoluble polymer.

The opaque layer must be fairly permeable to water, so that when it isdesired to remove the opaque coating, the film can simply be immersed inwater. Within a very short time the opaque layer falls away from thefilm in a single piece, rather than in small troublesome flakes.

This application is a division of US. patent application Ser. No.788,109, filed Oct. 28, 1968, now Pat. No. 3,598,- 591 which in turn isa continuation-in-part of US. patent application Ser. No. 645,032, filedJune 9, 1967 (now abandoned).

This invention relates to both photographic and radiographic sheets.More specifically, this invention relates to sensitized films having aunique, removable opaque coating and to specially coated polymericsheets from which such sensitized films can readily be manufactured.

In certain photographic applications, it is advantageous to removeexposed film from a camera and then simultaneously develop and print anappropriate photograph either immediately, or within a short timethereafter; this developing and printing generally (but not necessarily)being done outside the camera. Illustrative of this type of photographicprocess is the Well-known photograph-in-aminute (or even less time)involving a so-called film unit in which (after exposure of thesensitized emulsion layer in the camera) both the negative and positiveimages are simultaneously developed, usually shortly after exposure ofthe negative. Then the positive print or photograph (in color or inblack and white) can be stripped from the film unit as a practicallyfinished photographic product. One of the major shortcomings of thistype of process heretofore is that there has been available no practicalWay to preserve the transparent negative part of the film unit for reuseand/ or preservation of the precise photographic record.

Several requisites exist for such a reusable negative. One suchrequisite is that the sensitized film product have a coating on thereverse side of the film base (on the side opposite the sensitizedsurface) that is essentially opaque to actinic light. Such a coatingmust have an optical density of at least 6 (and preferably at leastabout 8) over the entire visible spectrum. In addition, the finalsensitized film product must be extremely thin (i.e., no more than about6 mils thick). Generally the sensitized product cannot be utilized inexisting film pack type photographic equipment of the most convenienttype unless its total thickness (including film base, sensitizedlayer(s), su pelloid, anti-static and/or anti-halation layer(s), andopaque backing) is less than about 6 mils. Usage of the product in suchfilm packs also requires that the film be extremely flexible. Thus, theopaque backing that is utilized must not only have excellentlight-absorbing properties, but it must also be very flexible; it mustadhere tightly to the sensitized film; and it must be extremelyresistant to flaking or breaking loose from the film base duringhandling, manufacture, exposure (in the camera), and development of thephotograph after exposure.

The necessity for the opaque backing can be readily appreciated when itis realized that the type of development to which such sensitized filmsare usually subjected involves (a) the removal of the film from thecamera after it is exposed (during which removal, a pod of developingreagents is squeezed, with the reagents being spread evenly across thesurface of the exposed film between the exposed sensitized surface and areceiver sheet), (b) the holding of the exposed film unit for a periodof time outside the camera (to permit the completion of the devslopmentof the image and concomitant transfer of the developed image to thereceiver sheet), and (c) finally the separation of the receiver sheet(containing the positive image) from the negative. Note that during thedeveloping period, the film unit is outside the camera. It is duringthis critical (development) period that the opaque backing is necessarybecause, while the receiver sheet can serve to protect the exposed,developing sensitive layer from incident light striking the film unitfrom one side, the sensitive layer must also be protected (during thecritical developing period) from extraneous light that strikes the filmunit from the reverse side. Conventional heavy paper or separate opaquelayers are either too bulky or too inflexible to be useful in the mannerrequired for the film units described above.

Two additional requirements that exist for the manufacture of acceptablefilm units for purposes such as those described above are (a) the opaquebacking must be removable in as short a time as possible (preferably inless than 1 minute) from the negative film base after it is developed,and (b) the opaque backing must be removable from such developednegative in a single piece (or at most a few large pieces).

-It has been discovered that all of the criteria set out above can bemet by utilizing a sensitized film that has been coated (on the sideopposite from the sensitized side) with two layers. The first layer(hereinafter termed the barrier layer or barrier coating) consistsessentially of a polymeric material that is soluble in water. Preferably(but not necessarily) such polymeric material should be insoluble inrelatively highly concentrated aqueous solutions. The second layer(hereinafter referred to as the opaque layer or coating) is (a)insoluble in water, (b) permeable to water, contains enough carbon tomake it practically impermeable to visible light, and (d) also containsa fairly high proportion of a polymeric material having the necessarytenacity (to hold together the opaque layer in the form of a film evenafter the polymeric material in the barrier layer has been dissolved inwater, thereby making it possible to strip this opaque layer from thebase in a single piece whenever it is desired to do so), as well as thenecessary flexibility (to be subjected to the sharp flexing that occursin the film pack inside the camera, for example, when the film is pulledor rolled over spacers and rollers having very limited clearances,without cracking, crazing or flaking during such flexing).

Thus, in the practice of one aspect of this invention, a film unithaving a negative portion comprising a light-sensitive layer, aconventional subbing layer, a polymeric film base, another conventionalsu layer, a clear, conventional pelloid layer, a barrier layer (inaccordance with the present invention), and an opaque layer (also inaccordance herewith), all in that order is first exposed and thendeveloped for the prescribed number of seconds to obtain the desiredphotograph. Then the negative (still containing intact the protectiveopaque layer and the barrier layer) can be transferred into a suitablestorage container in which it can be transported to a place where thenegative can be fixed under more convenient conditions. Actually at anyconvenient time after the development of the negative, the opaque layercan be removed simply by immersing the developed negative for a veryshort time into either a water bath or a dilute aqueous solution of somekind. In relatively pure water, the barrier layer immediately becomessoft and then dissolves, thereby permitting the opaque layer to beeasily stripped from the film base in a single piece. The fact that theopaque layer can be stripped from the film in a single piece is of greatsignificance because, heretofore, layers that were removable from filmduring the processing of the film generally either flaked from the filmin pieces of varying size that were often bothersome because it was verydiflicult to separate them from the film and from the processingsolutions, which in turn were diflicult to clean up. In the practice ofthe present invention, removed opaque layers remain in a single pieceand can thus be readily removed from the processing solutions. Thebarrier layer dissolves in the water bath but, since it is preferablycolorless, its presence in the solutions is not particularlytroublesome.

The drawings illustrate two embodiments of the final protectedsensitized film aspect of the present invention. In FIG. 1, for example,there is shown a polymeric film base having coated on one surfacethereof a sensitized layer, which can be any of a multitude ofconventional materials (for example, silver halide emulsions and thelike) having an ability to form latent, developable images when they areexposed to light or X-ray radiation. On the reverse side of the filmbase there are coated, in turn, a conventional pelloid layer (generallyapplied to minimize cur in the film caused by the sensitized layer), abarrier layer (in accordance with the following detailed description),and an opaque layer (which will also be described in detail below). Thepelloid layer is not essential, however, for the successful practice ofthis invention.

FIG. 2,".which illustrates a preferred embodiment of this inventionshows a typical photographic film having, in addition to the layersdescribed above, a final backing layer consisting of material having thedesired eifect of reducing or minimizing the frictional and blockingcharacteristics of the black layer of the film unit.

As it was stated hereinbefore, the barrier layers of this inventionconsist essentially of one or more polymers having the ability todissolve readily in water. The barrier layers also present the migrationof carbon (from the opaque layer) into the pelloid layer. However,useful polymers must also have the ability to cause the opaque layer (ofthe present invention) to adhere tenaciously to the film base and/0rpelloid layer (much as a sub causes a gelatin emulsion layer to adhereto the film base) during ordinary handling and storage. Also, thewater-soluble polymer must be of the type that produces relatively lowadhesion when it is wet with water. In addition it must be compatiblewith gelatin, forming a good bond with conventional gel type pelloids.Thus, not all water soluble polymers can be used successfully in thebarrier layers of the present invention. Also, it is essential that thepolymer that is present in the barrier layer in greatest amount becompatible with gelatin emulsions (ina test such as that illustrated inExample I, below). Still another test that this so-called barrierpolymer must meet successfully is an adhesion test involving theprocedure that is also detailed in Ex ample 1, below. Thus, acceptablebarrier" polymers must also be able to cause one of the opaque layers ofthe present invention to adhere tenaciously to the pelloid layer and/orthe film base itself. Acceptable barrier polymers, therefore, cangenerically be characterized as (a) being soluble in water (to levels ofat least about 5 weight percent);

(b) exhibiting 1% aqueous solution viscosities of at most about 10poises;

(c) being compatible with gelatin coatings;

((1) having molecular weights of at least about 50,000;

and

(e) causing one of the opaque" layers of this invention to adhere to thegelatin coating.

When the barrier and opaque coatings of this invention are directlysubjected to developer solutions and the like (-as for example when theyare used for coatings on radiographic or motion picture films) wherein,during at least the initial processing, it is preferred that the opaquecoating remains attached to the transparent negative, it will benecessary to impose still another requirement upon the barrier polymersthat are useful. Thus, preferred barrier polymers that are particularlyuseful in this type of development (wherein they are exposed toconcentrated aqueous solutions during a period of time when it ispreferred that they remain in place over the film) have the additionalrequirement that they be essentially insoluble in water solutionscontaining more than about 5 weight percent of dissolved ionizablematerial. Typical (nonlimiting) examples of acceptable barrier polymersinclude the commercially available hydroxypropyl celluloses, alkalimetal salts of ethyl celluose sulfate, copolymers of acrylic acid andethylacrylate, carboxymethyl celluloses, and alkila metal salts ofcopolymers of methyl acrylate and acrylic acid. An example of a materialthat is preferred in accordance with the foregoing general descriptionis sodium ethyl cellulose sulfate. Preferred alkali metal ethylcellulose sulfates are those containing from about 34 to about 40percent ethoxyl and from about 4 to about 7 percent combined sulfur, andhaving an intrinsic viscosity of from about 0.4 to about 0.8 (measuredin dimethyl sulfoxide+l% potassium iodide).

EXAMPLE I Barrier polymer tests In order to determine whether aparticular polymer has (a) the necessary compatibility with gelatin and(b) the necessary degree of adherence with one of the opaque coatings(which will be described in detail below) in order to be an acceptablebarrier polymer, the following test is performed:

First, more than about 5 weight percent solution of the polymer beingtested (in distilled water) is coated on either a conventional celluloseacetate or a conventional poly (ethyleneterephthalate) film base thathas been coated initially with about 0.2 mil thick layer of aconventional dried gel pelloid (about 0.09 pound of gelatin 6 rated poorin either test are generally considered to be unacceptable. Note thatcertain combinations of polymers actually yield better test results thando either of the individual polymers.

TAB LE I Polymer tested Dry adhesion and Wet compatibility strippingHydroxypropyl cellulose Sodium ethyl cellulose suli'ate Oarboxylatedacrylic copolyme Polyvinylpyrrolidone Polysaccharide 2 Ethyl cellulosephthalate (28% ethoxyl)... 7 Sodium salt of copolymer of ethylacrylateacrylic acid.

8 Polysaccharide 3 Carboxymethyl cellulose Sodium salt of methylacrylate-acrylic acid copolymer.

dium etyhl cellulose sul to.

% hydroxypropyl cellulose plus 50% soium ethyl cellulose sulfate. 21 67%hydroxypropyl cellulose plus 33% sodium ethylcellulose sulfate.

1 Sold by National Starch Company under the trade name Resyn 78-3205." 2Sold by Stein. Hall & Co, under the trade name Stractor." 3 Sold byStein, Hall & 00. under the trade name Polymer 705 D-A.

per 100 square feet). A totalof 1 pound of the solution of 6.3 percentbarrier polymer per 100 square feet is applied to the gel pelloid. It isthen dried in a circulating air drying oven at a temperature of about100 F. for about 13 minutes. Then a weight percent aqueoussolutionconsisting of the following:

Ingredient:

Parts by weight Carbon 4 Na ethylacrylate-acrylic acid copolymer 2 6Distilled water 87 Isopropyl alcohol 1.3 n-Butyl alcohol 1.3 Surfactant0.4

Average particle size of about 0.5 micron.

2 Intrinsic viscosity:O.7 (in methanol).

3 Na salt of alkylaryl polyether sulfate. is applied overthe barriercoating at a rate of 2.5 pounds of the solution per 100 square feet. It,too, is dried in the same manner as the barrier coating.

The resulting coated film is conditioned at a relative humidity of for24 hours and then scratched deeply with a sharp knife or razor blade.Across this scratch is pressed a piece of conventional pressuresensitive tape. The tape is immediately stripped quickly from thescratched surface and observed. If the prospective barrier polymer hasthe necessary compatibility and adherence qualities, no more than asmall amount of the opaque layer is removed along with the tape, whileunacceptable polymers (i.e., prospective barrier polymers) fail in thistest by permitting a large amount of the opaque coating to be strippedoff the film unit along with the tape. In Table I, below, is listedresults from a series of such dry adhesion and compatibility tests.

Table I also tabulates test data involving a so-called wet strippingtest in which a prospective barrier polymer must also performsuccessfully in order to be considered acceptable. This test involvessimply immersing an unscratched portion of the above-described test filmin room temperature water for 2 minutes, and then immediately trying topeel the opaque coating away from the film. Acceptable barrier polymersm-ust soften and effectively dissolve in the water, releasing the opaquecoating completely in this period of time. Optimum barrier polymers arerated good in both tests, while those The latter combinationsillustrated in Table I, above, include combinations of hydroxypropylcellulose and so dium ethyl cellulose sulfate, which combinations arealso particularly preferred embodiments of the present invention. Thus,barrier coatings that consists essentially of mixtures of hydroxypropylcellulose and alkali metal salts of ethyl cellulose sulfate containingat least about 15% (preferably at least about 25%) of alkali metal ethylcellulose sulfate have been found to perform in an optimum manner.

The opaque coating The opacity of the opaque layer or coatings of thepresent invention is preferably due to the presence in the layer of fromabout 10 to about 45 (and preferably between about 30 and about 40)weight percent of total solids of finely divided carbon (having anaverage ultimate particle size of less than 1 micron). This relativelylarge amount of carbon must be held together and bound to the barrierlayer or coating (described above) by means of one or more polymericmaterials having the following characteristics:

(1) In its coated condition it must be substantially insoluble in water.

(2) In one preferred embodiment of this invention, the opaque coatingpolymer must be initially soluble in water to the extent of at leastabout 5 weight percent.

(3) This preferred opaque coating polymer must also have the ability tobe convertible into a water insoluble polymeric coating after it isapplied in the form of an aqueous solution, for example by curing orbeing cross-linked.

(4) The viscosity of a water solution of such a preferred opaque layerpolymer (at a level of 5 weight percent in distilled water at 25 C.)must be at most about ;10 poises.

(5) The resulting water-insoluble opaque coating must be fairlypermeable to water, having the ability to permit water to pass throughit to dissolve the barrier polymer(s) without itself being broken up ordissolved.

(6) It must have a high degree of elasticity to both minimize curl andto hold itself together during the extreme bending and torsionconditions to which the final film units of the invention must besubjected. Hence,

it must have a Youngs modulus (in tension) between about 400 and about5000 pounds per square inch.

Of those polymeric materials meeting the above requirements, the alkalimetal salts (preferably sodium) of copolymers of ethyl acrylate andacrylic acid such as those made in accordance with the processesdescribed in 11.8. Pat. 3,062,674, having intrinsic viscosities of atleast about 0.3 in methanol (preferably within the range of from about0.5 to about 1) are particularly preferred. Intrinsic viscositiesdescribed herein are measured at 25 C.

In the opaque coatings of this invention, the weight ratio of polymer tocarbon can be varied to some extent, depending somewhat upon theparticular particle size of the carbon that is dispersed through thepolymeric material. However, generally the weight ratio of polymer tocarbon in this opaque" coating should be within the range of from about1.2 to l to about 9 to l, and preferably should be within the range offrom about 3 to 2 to about 2.3 to 1, respectively. If desired, mixturesof polymers can also be used in this opaque layer to achieveparticularly desired results. Other materials such as plasticizers,cross-linking agents, dyes (and even con- 'ventional Intensifiers whenthe film unit, for example, is designed for use for radiography workwith X-rays), and the like can also be present in the opaque coatings ofthis invention, so long as relatively minor amounts of such materialsare utilized. In any event, the opaque coating polymer(s) must make upat least 50 Weight percent (preferably at least about 60 weight percent)of the opaque coating. The total weight of the opaque coating can alsovary over a fairly wide range. However, to meet the stringentrequirements of the usage detailed above (relating to the film packs),the opaque coating should be at most about 1 mil in thickness and bepresent in amounts ranging from about 0.2 to about 0.8 pound per 100square feet of ifilm surface (when, for example, it is on only one sideof the film).

In Example 2, below, the application of an opaque coating consistingessentially of the particularly preferred sodium salt of ethylacrylate-acrylic acid copolymers is detailed. Note that in all of thepresent examples, all parts given are by weight unless otherwisespecified.

EXAMPLE 2 LA polymer solution is prepared by stirring together thefollowing in a conventional mixing vessel:

Ingredient: Parts Distilled water 86 Polymer Isopropyl alcohol 2 n-Butylalcohol 2 Surfactant (wetting agent) 0.4

Sodium salt of copolymer of ethyl acrylate and acrylic acid (intrinsicviscosity of 0.7 in methanol).

2 Sodium salt of alkyl aryl polyether sulfonate.

Into the resulting solution are then slowly added 7 parts of carbonblack the particles of which have a mean diameter of about 22millimicrons. This dispersion is then milled for 90 minutes in aconventional high intensity dispersion mill and then diluted furtherwith 70 parts of distilled water. Just before the opaque layer isapplied to the film, 0.5 part of 1, 4 butanediol diglycidyl ether (a hisepoxide) a cross-linking agent (used for its ability to react with thepolymer to thereby convert it into a water-insoluble form) is stirredinto the black dispersion. If desired, any other reactive cross-linkingagent such as polyaziridine can be used either with the his epoxide, orin place of it. The resulting dispersion, which has a viscosity at roomtemperature of about 100 centipoises, is coated over the barrier layerof Example I at a rate of 2.5 pounds per 100 square feet of filmsurface, and then dried for 10 minutes at a temperature of 105 F. Thethickness of the resulting dry opaque coating is only 0.3 mil. Yet itsoptical density through the entire visible spectrum is more than 8.5.

Upon being immersed in distilled water for 30 seconds the opaque coatingis readily removable in a single piece. Film units made from the coatedfilm perform satisfactorily in a conventional film pack type camera,having excellent flexibility and exhibiting essentially no crazing orflaking in actual use.

It should be noted that, while it is preferred that the opaque coatingof the present invention be applied over the barrier coating by means ofaqueous solutions of the mixtures of polymer(s), carbon, and otheradditives (where desired or appropriate), they can also be applied viaconventional organic solvent techniques, in which the polymer isdissolved in the organic solvent (such as, for example, butyl alcohol,methyl ethyl ketone, methylene chloride, ethyl alcohol, xylene,perchloroethylene, and the like, as well as mixtures thereof). Byutilizing such organic solvent techniques polymers that are suitable foruse as opaque coating polymers (as described above) that are notinitially soluble in water can be used. Cellulose acetate is an exampleof such useful water insoluble polymers that have the necessaryfunctional properties (as outlined hereinbefore) to be acceptable as themajor component in the opaque coating, but which is not initiallysoluble in water. In the case of cellulose acetate, a preferred organicsolvent for its application over the barrier" coating is a mixture ofacetone and methyl or ethyl alcohol. When organic solvents are used, thecarbon can simply be well dispersed through the solvent system by any ofseveral well-known methods before the coating is applied. Then, theorganic solvent is simply evaporated from the coated surface to yieldthe desired opaque coating. In view of the broad knowledge in the artregarding organic solvent systems for various polymers, it is believedthat a detailed discussion herein of this particular procedure ofapplying the opaque and barrier coatings of this invention is notnecessary.

EXAMPLE II A solution of parts of cellulose acetate (acetyl content of40%, intrinsic viscosity in acetone of 1.2) in a mixture of 1440 partsof acetone and parts of methanol is prepared by simply stirring theingredients together at about 35 C. for 2 hours. To the resultingsolution are added 300 parts of carbon black. The suspension of carbonin organic solvent is milled in a conventional Kady type high intensitymill for 15 minutes. To this solution is added 200 additional parts ofthe cellulose acetate (dissolved in a mixture of 900 parts of acetoneand 100 parts of methanol). The resulting susepnsion is then coated (ata rate of 2 pounds of the 10.3 weight percent solution per 100 squarefeet of film surface) on the film coated with the barrier coating ofExample I above and dried immediately. The wet stripping and dryadhesion properties of the resulting coated film is excellent.

EXAMPLE III A film unit having an opaque coating is prepared as inExample II above, except that additionally, 30 parts of diethylphthalate (a plasticizer) are dissolved into the coating solution beforeit is applied to the film. The resulting film also has excellent dryadhesion and Wet stripping properties.

Apparently, the presence of so much carbon of such very small particlesize in the opaque layer contributes considerably to the necessary waterpermeability of the opaque layers of this invention. This can be morereadily appreciated when it is realized that cellulose ester coatings,per se, are fairly water-impermeable. Yet, with the carbon contents ofthe present invention, adequate water permeability of the resultingopaque layer results. Hence, while adequate water permeability is animportant criterion for the opaque coatings of this invention, suchpermeability is practically assured when at least the pre- Material:Parts Polymethacrylate beads 1 10 Carbon black 2 12 /2 second cellulosenitrate 12 Acetone 300 Methyl alcohol 675 Average particle diameter=5microns; modified with 5% divinyl benzene; prepared as in U.S. Pat.2,701,245.

.flMean particle diameter equals about 100 mlllimicrons. This coatingsolution (a dispersion of carbon and beads in a solution of cellulosenitrate) is coated at a rate of 8 pounds per 1000 square feet of filmsurface. The resulting coated film is dried for 2 minutes in a dryingoven at a temperature of 250 F. The frictional properties of film unitsmade from the resulting coated film are excellent, and are significantlybetter (i.e. the friction generated between sheets of film in aconventional film pack is lower) than those of film units that do nothave the last coating.

Anti-friction and anti-blocking coatings While film units having thebarrier and the opaque coatings of the present invention generallyperform well in the film packs described above, it has been found thatthe frictional properties of such film units can be still furtherimproved by utilizing a thin additional coating (over the opaquecoating) of an anti-friction coating such as those described in detailin U.S. patent application Ser. No. 596,803, filed Nov. 25, 1966 or inU.S. Pat. No. 3,295,979. In this patent appplication are describedcoatings that are comprised of a blend of (a) from about 0.5 to about 10percent of substantially spherical polymeric beads having averagediameters of from about 0.5 to about 25 microns; (b) from about 0.3 toabout 8 percent of low viscosity cellulose nitrate, and (c) from about0.3 to about 8 percent of finely divided carbon; all of which can becoated from an organic solvent system. For the purpose of detailing thepreferred anti-friction coating portion of some of the preferred filmunits of this invention, the disclosure of U.S. Ser. No. 596,803, filedNov. 25, 1966, is hereby incorporated by reference into the presentdisclosure. It should be noted, however, that the presence of such ananti-friction coating is not necessary for the successful practice ofthe present invention.

In U.S. Pat. No. 3,295,979 are described coatings that are composed of(a) casein, (b) 1-10%, based on the dry weight of the casein, of acompound having the formula:

wherein R is an aliphatic hydrocarbon group containing from 10 to 18carbon atoms, R is selected from the group consisting of hydrogen andaliphatic hydrocarbon groups containing from 10 to 18 carbon atoms, and

CH CH COOM and M is either H or a cation, and sometimes (C) from about 1to about 3% based on the dry weight of the casein, of a matting agent ora chemical hardener; all of which can be coated in accordance with theprocesses described in U.S. Pat. 3,295,979, the disclosure of which ishereby incorporated by reference into the present disclosure.

EXAMPLE V In accordance with the procedures detailed above, a 5

mil cellulose acetate film support is coated successively with thefollowing layers (each layer being dried before the next is applied):(a) gelatin (40 grams/ sq. ft.){+ formaldehyde (0.4 g./100 sq. ft.), (b)hydroxypropyl cellulose (7 g./100 sq. ft.)+sodium ethyl cellulosesulfate (15 g./100 sq. it), (c) ethyl acrylate/acrylic acid copolymer(60 g./100 sq. ft.)+carbon black (40 g./100 sq. ft.)'+1,4-butanediol-diglycidyl ether (5 mg./ 100 sq. ft.) and (d) casein(10 g./100 sq. ft.), N-tallow-beta-amino-dipropionate (0.4 g./ 100 sq.ft.), polymethacrylate beads (75 mg./100 sq. ft), and dioctylsulfosuccinate (0.2 g./ 100 sq. ft.). On the reverse side of thecellulose acetate film support are coated (1) a conventionalpanchromatically sensitized high speed silver bromoiodide gelatinemulsion and (2) a conventional gelatin overcoat. I

Layer or coating ((1) in Example V is typical of the friction reducing,anti-static treatments set out in the disclosure of U.S. Pat. No.3,295,979. The wet stripping and dry adhesion properties of theresulting coated film is excellent.

As it was indicated at the outset of this disclosure, the coatings ofthe present invention are also useful as photographic film coatings forsensitized films other than the film units. Thus, they can serve toprotect, for example, X-ray or other radiographic film from visiblelight, and can, of course, be readily removable from such films insingle units when such removal is desired. They can also serve toprotect motion picture film from incident light where extra backingprotection from light might be needed temporarily, until the film isdeveloped. In the case of X-ray films, the permeability of the opaquecoating will permit developers to pass through the black coating andcarry out the development of the exposed film to a significant extentbefore the opaque coating is removed. When the preferred barrier layersof this invention are used (wherein the polymer(s) are not soluble inconcentrated aqueous solutions) the development can be completed whilethe opaque and barrier layers of this invention remain essentiallyintact. However, these coatings can be removed quickly when such removalis desired by simply rinsing or immersing the developed film with eitherpure water or a relatively dilute aqueous solution. The amount ofpolymeric materials in the barrier layers of the coated films of thisinvention can vary considerably, but should generally be within therange of from about 0.03 to about 2 pounds per 100 square feet ofindividual film surface covered thereby, and preferably should be withinthe range of from about 0.04 to about 0.1 pound per 100 square feet.

We claim:

1. An article of manufacture comprising a polymeric film base havingover at least one surface thereof a multiple-layer coating; saidmultiple-layer coating comprising (a) a first barrier layer consistingessentially of at least one water soluble polymer that is compatiblewith gelatin and provides, in the dry state only, a tight bond betweensaid film base sheet and the opaque layer (b) below, and is insoluble inwater solutions containing more than 5 weight percent of dissolvedionizable material; and

(b) an opaque layer that is (1) substantially impervious to visiblelight, (2) insoluble in water, and (3) permeable to liquid water whensaid article is contacted with said water; said opaque layer consistingessentially of a blend of finely divided carbon and at least onewater-insoluble organic polymer having a high degree of elasticity andthe amount of said water-insoluble organic polymer in said blend beingat least about 50 weight percent of said blend.

2. An article of manufacture as in claim 1, wherein said barrier layerconsists essentially of a member of the group consisting of alkali metalsalts of ethyl cellulose sulfates, hydroxylpropyl celluloses, alkalimetal salts of acrylic acid/ethylacrylate copolymers,carboxymethylcelluloses, alkali metal salts of methyl acrylate/acrylicacid copolymers, and mixtures thereof; and wherein said opaque layerconsists essentially of a blend of said finely divided carbon and amember selected from the group consisting of cellulose esters,cross-linked ethyl acrylate/ acrylic acid copolymers having an intrinsicviscosity in methanol of at least about 0.3 and mixtures thereof.

3. An article of manufacture as in claim 1, wherein said barrier layerconsists essentially of a blend of sodium ethyl cellulose sulfate andhydroxypropyl cellulose; the amount of said sodium ethyl cellulosesulfate in said blend being at least about 15 Weight percent and theamount of said blend being from about 0.03 to about 2 pounds per 100square feet of said article of manufacture.

4. An article of manufacture as in claim 3, wherein the weight ratio ofsaid sodium ethyl cellulose sulfate to 1 said hydroxypropyl cellulose isfrom about 1:2 to about 2: 1, respectively.

5. An article of manufacture as in claim 3, wherein said opaque layerconsists essentially of from about 10 to about 45 weight percent ofcarbon having an average 12 particle diameter of at most about 1 micronand at least about 60 weight percent of said water-insoluble organicpolymer. 7

References Cited UNITED STATES PATENTS 1,116,479 111/1914 Planchon96-434 1,994,875 3/1935 Schneider et al 96-84 2,319,080 5/1943 Nadeau etal 96-84 3,237,008 2/1966 Dostes et a1. 96-84 3,295,979 1/1967 Secristet al. 96-87 FOREIGN PATENTS 633,936 12/1949 Great Britain 9684 129,9245/1955 Great Britain 9684 RONALD H. SMITH, Primary Examiner

